WO2021215407A1 - Composition de résine durcissable et procédé de fabrication d'un objet tridimensionnel au moyen de cette composition - Google Patents

Composition de résine durcissable et procédé de fabrication d'un objet tridimensionnel au moyen de cette composition Download PDF

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WO2021215407A1
WO2021215407A1 PCT/JP2021/015915 JP2021015915W WO2021215407A1 WO 2021215407 A1 WO2021215407 A1 WO 2021215407A1 JP 2021015915 W JP2021015915 W JP 2021015915W WO 2021215407 A1 WO2021215407 A1 WO 2021215407A1
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resin composition
mass
curable resin
polymerizable compound
meth
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PCT/JP2021/015915
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Japanese (ja)
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恭平 和田
卓之 平谷
涼 小川
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キヤノン株式会社
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    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F265/00—Macromolecular compounds obtained by polymerising monomers on to polymers of unsaturated monocarboxylic acids or derivatives thereof as defined in group C08F20/00
    • C08F265/04—Macromolecular compounds obtained by polymerising monomers on to polymers of unsaturated monocarboxylic acids or derivatives thereof as defined in group C08F20/00 on to polymers of esters
    • C08F265/06—Polymerisation of acrylate or methacrylate esters on to polymers thereof
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F279/00—Macromolecular compounds obtained by polymerising monomers on to polymers of monomers having two or more carbon-to-carbon double bonds as defined in group C08F36/00
    • C08F279/02—Macromolecular compounds obtained by polymerising monomers on to polymers of monomers having two or more carbon-to-carbon double bonds as defined in group C08F36/00 on to polymers of conjugated dienes
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F283/00—Macromolecular compounds obtained by polymerising monomers on to polymers provided for in subclass C08G
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F283/00—Macromolecular compounds obtained by polymerising monomers on to polymers provided for in subclass C08G
    • C08F283/12—Macromolecular compounds obtained by polymerising monomers on to polymers provided for in subclass C08G on to polysiloxanes
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F285/00—Macromolecular compounds obtained by polymerising monomers on to preformed graft polymers
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F290/00—Macromolecular compounds obtained by polymerising monomers on to polymers modified by introduction of aliphatic unsaturated end or side groups
    • C08F290/02—Macromolecular compounds obtained by polymerising monomers on to polymers modified by introduction of aliphatic unsaturated end or side groups on to polymers modified by introduction of unsaturated end groups
    • C08F290/06—Polymers provided for in subclass C08G

Definitions

  • the present invention relates to a curable resin composition and a method for producing a three-dimensional object using the curable resin composition.
  • the cured resin layer is integrally laminated.
  • An optical three-dimensional modeling method (hereinafter referred to as a stereolithography method) is known.
  • the liquid surface of the liquid photocurable resin composition contained in the container is irradiated with light such as an ultraviolet laser to determine a predetermined value.
  • a cured resin layer is formed by curing with a thickness and a desired pattern.
  • a photocurable resin composition corresponding to one layer of the cured resin layer is supplied onto the cured resin layer, and the same is applied to the cured resin layer to be continuous with the previously formed cured resin layer.
  • a new cured resin layer is laminated and formed.
  • the stereolithography method is being applied to the modeling of prototypes for shape confirmation (rapid prototyping), the modeling of working models for functional verification, and the modeling of molds (rapid touring). Furthermore, in recent years, the use of stereolithography has begun to expand to the manufacture of actual products (rapid manufacturing).
  • Patent Document 1 discloses a curable resin composition containing a urethane (meth) acrylate oligomer, a radically polymerizable compound, and rubber particles, and has impact resistance due to the combined use of a flexible urethane oligomer component and rubber particles. Improvements are being considered.
  • Patent Document 1 since the viscosity of the radically polymerizable compound itself containing the urethane (meth) acrylate oligomer is high, the viscosity is further increased in order not to impair the workability at the time of producing the cured product by the stereolithography method. It was necessary to keep the amount of rubber particles added low. Therefore, it has been difficult to sufficiently improve the impact resistance.
  • the resin composition has a high viscosity, the supplyability of one layer of the curable resin composition deteriorates, and the yield of modeling deteriorates.
  • An object of the present invention is to provide a low-viscosity curable resin composition capable of obtaining a cured product having excellent impact resistance.
  • the curable resin composition of the present invention is Core-shell type rubber particles (A) and A radically polymerizable compound (B) having one or more radically polymerizable functional groups in the molecule, and A curable resin composition containing a radical polymerization initiator (C).
  • the core-shell type rubber particles (A) have a core layer and a shell layer containing a polymer having a heterocyclic structure.
  • the content of the radically polymerizable compound (B) is 50% by mass or more and 99% by mass or less, and is radically polymerizable with a molecular weight of 500 or more, when the total of all the components of the curable resin composition is 100% by mass. It is characterized by containing the compound (b-1) in an amount of 2% by mass or more and 70% by mass or less.
  • the present invention it is possible to form a cured product having excellent impact resistance, and it is possible to provide a curable resin composition having a low viscosity and excellent workability at the time of producing the cured product.
  • the core-shell type rubber particles (A) have a core layer and a shell layer containing a polymer having a heterocyclic structure.
  • the core-shell type rubber particles (A) have a core layer and a shell layer containing a polymer having a heterocyclic structure.
  • the type of polymer particles containing a rubber-like elastic body as a core layer is not particularly limited.
  • the preferable polymer constituting the rubber-like elastic body to be the core layer for example, at least two kinds selected from butadiene rubber, styrene / butadiene copolymer rubber, acrylonitrile / butadiene copolymer rubber, and styrene / butadiene / acrylonitrile / methyl methacrylate are selected.
  • Copolymerized rubber saturated rubber obtained by hydrogenating or partially hydrogenating these diene rubbers, crosslinked butadiene rubber, isoprene rubber, chloroprene rubber, natural rubber, silicon rubber, ethylene / propylene / diene monomer ternary copolymer rubber , Acrylic rubber, silicone / acrylic composite rubber, urethane rubber and the like. These polymers may be used alone or in combination of two or more.
  • copolymerized rubber acrylic rubber, and silicone obtained by copolymerizing at least two kinds selected from butadiene rubber, crosslinked butadiene rubber, styrene / butadiene copolymer rubber, and styrene / butadiene / acrylonitrile / methyl methacrylate. / At least one selected from acrylic composite rubber and urethane rubber is particularly preferable.
  • the glass transition temperature of the polymer constituting the core layer is preferably less than 20 ° C. When the glass transition temperature is less than 20 ° C., it is preferable because it easily functions as a shock absorber in the cured product at room temperature.
  • the shell layer contains a polymer having a heterocyclic structure such as a polymer having a heterocyclic group in the side chain.
  • a shell containing a polymer of a radically polymerizable compound such as a radically polymerizable compound having a heterocyclic structure and a dical polymerizable compound that polymerizes to form a heterocyclic structure on the surface of the polymer particles serving as a core layer. It has a layered structure.
  • the polymer having a heterocyclic structure forming the shell layer covers a part or the whole of the surface of the core layer by graft polymerization via a chemical bond or adsorption via a physical bond on the surface of the core layer. It is preferable to have.
  • the core-shell type rubber particles obtained by graft-polymerizing the shell layer onto the core layer can be formed by graft-polymerizing a radical-polymerizable compound by a known method in the presence of the particles to be the core layer.
  • a radical polymerizable compound which is a component of a shell layer to latex particles dispersed in water, which can be prepared by emulsion polymerization, mini-emulsion polymerization, suspension polymerization, etc. be able to. If there are no or extremely few reactive sites such as ethylenically unsaturated groups on the surface of the core layer from which the shell layer can be graft-polymerized, particles having an intermediate layer containing the reactive sites as the core layer will be used as the core layer.
  • the shell layer may be graft-polymerized after being provided on the surface of the above.
  • the form of the core-shell type rubber particles includes a form in which a shell layer is provided in the core layer via an intermediate layer.
  • the core-shell type rubber particles in which the shell layer is physically adsorbed on the core layer can be formed by polymer coating by a known method in the presence of the particles to be the core layer. For example, it can be produced by dissolving a polymer in a solution in which particles serving as a core layer are dispersed and adsorbing the polymer.
  • the heterocyclic structure of the shell layer has a heteroatom having a lone pair of electrons. Due to the effect of these heteroatoms, the solubility of the radically polymerizable compound (b-1) having a molecular weight of 500 or more, which will be described later, is improved.
  • the component (b-1) has a polar group of urethane bond, ester bond, carbonate bond or amide bond, preferably one or more of urethane bond, carbonate bond and ester bond. Heteroatoms inhibit the orientation of these bonds, resulting in a reduction in viscosity.
  • the heteroatom is incorporated into the cyclic structure of the heterocycle, the steric bulkiness around the lone electron pair of the heteroatom is reduced, so that the polarity is higher than that when the heteroatom is incorporated into the linear structure. Inhibition of group orientation is likely to occur.
  • the radically polymerizable compound containing a heterocyclic structure used for forming the shell layer has a cyclic skeleton having one or more heteroatoms represented by nitrogen atoms, oxygen atoms, sulfur atoms and the like.
  • the radically polymerizable compound that can be used in the shell layer preferably has a structure represented by the formula (1).
  • the hydrogen atom on the heterocycle or the substituent is an oxygen atom, a nitrogen atom, or a sulfur atom.
  • And may be linked to a radically polymerizable functional group typified by a (meth) acryloyl group, a vinyl group or the like.
  • A represents a radically polymerizable compound typified by a (meth) acryloyl group, a vinyl group, or the like.
  • Het represents a heterocycle.
  • X is a linking group that binds A and Het, and represents a hydrocarbon group that can have a hetero atom represented by an oxygen atom, a nitrogen atom, and a sulfur atom. X may be only a hetero atom.
  • the bond other than the bond that bonds A and Het may be bonded to, for example, a hydrogen atom, an alkyl group, an aromatic group, a heterocycle, a halogen, or the like. Good, but not particularly limited.
  • the bonder other than the bonder that binds A and Het is preferably bonded to a hydrogen atom, a methyl group, an ethyl group or a phenyl group.
  • the bond on nitrogen the case where two bonds other than the bond that binds to A are bound to the same heterocyclic structure is also included in the structure represented by the formula (1).
  • heterocyclic group containing only a nitrogen atom as a hetero atom as Het include residues of a monocyclic saturated heterocycle such as aziridine, azetidine, pyrrolidine, piperidine, piperazine, and pyrazoline; pyrrolin, pyrrole, 2,5-. Pyrrole such as dimethylpyrrole, pyrazole, 2-methylpyrazole, pyrazole such as 3-methylpyrazole, imidazole, imidazoline, imidazolidone, triazole, 1,2,3-triazole, 1,2,4-triazole, tetrazole, etc.
  • a monocyclic saturated heterocycle such as aziridine, azetidine, pyrrolidine, piperidine, piperazine, and pyrazoline
  • pyrrolin pyrrole
  • Pyrrole such as dimethylpyrrole, pyrazole, 2-methylpyrazole, pyrazole such as 3-methylpyrazole, imidazole
  • Residues of membered ring-based unsaturated heterocycles include 6-membered pyrimidines such as pyridine, pyridazine, pyrimidine, 6-methylpyrimidine, pyrazine, 1,2,4-triazine, 1,3,5-triazine, tetrazine, melamine, etc.
  • Residues of cyclic unsaturated heterocycles include indazole, indolin, isoindrin, indole, indolidine, benzoimidazole, quinoline, isoquinoline, 5,6,7,8-tetrahydro (3-methyl) quinoxalin, 3-methylquinoxalin, etc.
  • Residues of fused bicyclic heterocycles such as quinoxalin, quinazoline, cinnoline, phthalazine, naphthylidine, purine, pteridine, benzopyrazole, benzotriazole, benzopiperidin; Included are ring heterocyclic residues.
  • heterocyclic group containing only an oxygen atom as a hetero atom as Het examples include a monocyclic saturated complex such as oxylane, oxetane, tetrahydrofuran, tetrahydropyran, 1,3-dioxane, 1,4-dioxane, and 1-cyclopentyldioxolane.
  • Ring residues dicyclic saturated heterocyclic residues such as 1,4-dioxaspiro [4.5] decane, 1,4-dioxaspiro [4.5] nonane; ⁇ -acetolactone, ⁇ -propiolactone Residues of lactone-based heterocycles such as ⁇ -butyrolactone and ⁇ -valerolactone; residue of 5-membered ring-based unsaturated heterocycles such as furan, 2,3-dimethylfuran, and 2,5-dimethylhydrofuran.
  • Residues of 6-membered ring-based unsaturated heterocycles such as 3,4-dihydro-2H-pyran, 3,6-dihydro-2H-pyran; benzopyran, benzo such as benzofuran, isobenzofuran, 4-methylbenzopyran
  • Residues of fused bicyclic heterocycles such as dioxol, chroman, isochroman
  • residues of fused tricyclic heterocycles such as xanthene and dibenzofuran
  • residues of compounds containing cyclic ethers shown below can be mentioned.
  • heterocyclic group containing only the sulfur atom as a hetero atom as Het include residues of a 5-membered ring-based saturated heterocycle such as dithiolane; thian, 1,3-dithian, 2-methyl1,3-dithian and the like. Residues of 6-membered ring-based saturated heterocycles; 5-membered ring-based unsaturated heterocycles such as thiophene, 3-methylthiophene, 2-carboxythiophene, thiophene 1-oxide, thiophene 1,1-dioxide, and 4H-thiopyran.
  • heterocyclic group containing a nitrogen atom and an oxygen atom as heteroatoms as Het examples include morpholin, 2-pyrrolidone, 2-methyl-2-pyrrolidone, 2-piperidone, 2-methyl-2-piperidone, hydantin and pyrazolone.
  • Residues of monocyclic saturated heterocycles such as oxazole; oxazole, oxazole such as 4-methyloxazole, isooxazole, 2-methylisoxazole, isooxazole such as 3-methylisoxazole, 1,2,4-oxadi Residues of monocyclic unsaturated heterocycles such as azole; Ring residues; residues of fused tricyclic heterocycles such as phenoxazine; and the like.
  • heterocyclic group containing a nitrogen atom, an oxygen atom, and a sulfur atom as a hetero atom as Het include residues such as thiazole, isothiazole, thiadiazole, benzothiazole, thitriazole, phenothiazine, and thiazine.
  • Examples of the substituent on the heterocyclic group include a hydroxyl group, a thiol group, an amino group, a carboxy group, an isocyanate group, an epoxy group, an alkoxysilyl group and the like.
  • Examples of such a substituent include an alkyl group such as a methyl group, an ethyl group, an (iso) propyl group and a hexyl group; an alkoxy group such as a methoxy group, an ethoxy group and an (iso) propoxy group; a fluorine atom and a chlorine atom.
  • a group composed of a halogen atom such as a bromine atom and an iodine atom; a cyano group; an amino group; an aromatic hydrocarbon group; an ester group; an ether group; an acyl group; a thioether group; and the like can also be used. Further, the substitution positions of these substituents are not particularly limited, and the number of substituents is also not limited.
  • glycidyl and oxetane have an effect of reducing the viscosity, but the cyclic structure tends to be easily broken by heat, which is not so preferable from the viewpoint of storage stability of the resin composition.
  • Examples of the dical-polymerizable compound that polymerizes to form a heterocyclic structure include compounds that form a heterocycle exemplified as Het by polymerization, and examples thereof include methyl ⁇ -allyloxymethylacrylate.
  • the other radically polymerizable compound used for forming the shell layer is not particularly limited, but a monofunctional radically polymerizable compound having one radically polymerizable functional group in the molecule may be preferably used.
  • the monofunctional radically polymerizable compound can be appropriately selected from the viewpoint of compatibility with the core layer and dispersibility in the resin composition, and is 1 from the compounds exemplified as the component (B) described later. Species or a combination of two or more may be used.
  • a polyfunctional radically polymerizable compound may be used in combination.
  • the polyfunctional radical-polymerizable compound is preferably 0 parts by mass or more and 40 parts by mass or less with respect to 100 parts by mass of the radical-polymerizable compound used for forming the shell layer. Further, 0 parts by mass or more and 30 parts by mass or less is more preferable, and 0 parts by mass or more and 25 parts by mass or less is particularly preferable.
  • the content of the polyfunctional radically polymerizable compound is 40 parts by mass or less, the effect of improving the impact resistance by adding the core-shell type rubber particles (A) can be easily obtained.
  • the polyfunctional radically polymerizable compound can be appropriately selected from the viewpoint of compatibility with the core layer and dispersibility in the resin composition, and is 1 from the compounds exemplified as the component (B) described later. Species or a combination of two or more may be used.
  • the ratio of the radical-polymerizable compound having a heterocyclic structure and the dical-polymerizable compound which polymerizes to form a heterocyclic structure in the polymer of the radical-polymerizable compound forming the shell layer is the radical-polymerizable compound forming the shell layer. It is preferably 2 parts by mass or more and 100 parts by mass or less, and more preferably 5 parts by mass or more and 100 parts by mass or less with respect to 100 parts by mass of the polymer.
  • the ratio of the radical polymerizable compound having a heterocyclic structure and the dical polymerizable compound to be polymerized to form a heterocyclic structure satisfies the above range, the increase in viscosity when contained in the curable resin composition is more effective. Can be suppressed.
  • the ratio of the core layer to the shell layer in the core-shell type rubber particles (A) is preferably 1 part by mass or more and 200 parts by mass or less, more preferably 2 parts by mass, with respect to 100 parts by mass of the core layer. It is 180 parts by mass or less.
  • the mass ratio of the core layer and the shell layer is within the above range, the effect of improving the impact resistance and the effect of reducing the increase in viscosity by containing the core-shell type rubber particles (A) can be sufficiently obtained.
  • the shell layer is 1 part by mass or more, the dispersibility in the curable resin composition is sufficient, and the effect of improving the impact resistance and the effect of reducing the increase in viscosity can be easily obtained.
  • the shell layer is 200 parts by mass or less, a sufficient effect of improving impact resistance can be obtained without adding a large amount of core-shell type rubber particles, so that the viscosity of the curable resin composition is appropriate. Yes, it is easy to handle.
  • the core-shell type rubber particles (A) preferably have an average particle size of 20 nm or more and 2 ⁇ m or less, and more preferably 50 nm or more and 1 ⁇ m or less.
  • the average particle size of the core-shell type rubber particles (A) can be measured by using a dynamic light scattering method. For example, the rubber particles can be dispersed in a suitable organic solvent and measured using a particle size distribution meter.
  • the content of the core-shell type rubber particles (A) in the curable resin composition is preferably 7 parts by mass or more and 65 parts by mass or less, more preferably 10 parts by mass with respect to 100 parts by mass of the radically polymerizable compound (B). It is 60 parts by mass or less.
  • the content of the core-shell type rubber particles (A) is within the above range, the effect of suppressing the increase in viscosity of the curable resin composition is remarkably exhibited.
  • the content of the core-shell type rubber particles (A) is 7 parts by mass or more, entanglement between the particles in the resin composition is unlikely to occur via the shell layer, so that the effect of the increase in viscosity due to the addition of the particles is small, and in addition, It is easy to obtain the effect of improving impact resistance.
  • the content of the core-shell type rubber particles (A) is 65 parts by mass or less, forced proximity between the particles in the curable resin composition is unlikely to occur, and the viscosity is reduced by including the heterocyclic structure in the shell layer. The effect is easily obtained, and the appropriate viscosity makes it easy to handle.
  • the radically polymerizable compound (B) is a radically polymerizable compound having one or more radically polymerizable functional groups in the molecule.
  • the content of the radically polymerizable compound (B) is 50% by mass or more and 99% by mass or less when the total of all the components of the curable resin composition is 100% by mass.
  • the radically polymerizable compound (B) contains 2% by mass or more and 70% by mass or less of the radically polymerizable compound (b-1) having a molecular weight of 500 or more, assuming that the total of the radically polymerizable compounds (B) is 100% by mass. ..
  • the radically polymerizable compound (B) preferably contains a radically polymerizable compound (b-2) having a molecular weight of less than 500.
  • a radically polymerizable compound (b-2) having a molecular weight of less than 500 include a monofunctional (meth) acrylic acid ester and a monofunctional (meth) acrylamide derivative.
  • the molecular weight is preferably a weight average molecular weight.
  • Examples of the radically polymerizable functional group include ethylenically unsaturated groups.
  • Specific examples of the ethylenically unsaturated group include a (meth) acryloyl group, a vinyl group, and a maleimide group.
  • a (meth) acryloyl group means an acryloyl group or a methacryloyl group.
  • Examples of the radically polymerizable compound having a (meth) acryloyl group include (meth) acrylamide-based compounds and (meth) acrylate-based compounds.
  • Examples of monofunctional (meth) acrylamide-based compounds having one radically polymerizable functional group in the molecule include (meth) acrylamide, N-methyl (meth) acrylamide, N-isopropyl (meth) acrylamide, and N-tert-.
  • Examples of the monofunctional (meth) acrylate-based compound having one radically polymerizable functional group in the molecule include methyl (meth) acrylate, ethyl (meth) acrylate, n-butyl (meth) acrylate, and isobutyl (meth).
  • isobornyl (meth) acrylate, dicyclopentanyl (meth) acrylate, dicyclopentenyl (meth) acrylate, cyclohexyl (meth) acrylate, 2-methyl-2-adamantyl (meth) acrylate, 2-ethyl-2. -Adamantyl (meth) acrylate, etc. can be mentioned.
  • Examples of the monofunctional radical polymerizable compound having an ethylenically unsaturated group other than the (meth) acryloyl group include styrene derivatives such as styrene, vinyltoluene, ⁇ -methylstyrene, chlorostyrene, styrenesulfonic acid and salts thereof.
  • Maleimides such as maleimide, methylmaleimide, ethylmaleimide, propylmaleimide, butylmaleimide, hexylmaleimide, octylmaleimide, dodecylmaleimide, stearylmaleimide, phenylmaleimide, cyclohexylmaleimide, vinyl acetate, vinyl propionate, vinyl pivalate, benzoic acid
  • Vinyl esters such as vinyl and vinyl silicate, vinyl cyanide compounds such as (meth) acrylonitrile, N-vinylpyrrolidone, N-vinylcaprolactam, N-vinylimidazole, N-vinylmorpholine, N-vinylacetamide and the like. -Examples include vinyl compounds.
  • These monofunctional radically polymerizable compounds may be used alone or in combination of two or more.
  • a monofunctional radically polymerizable compound when a monofunctional radically polymerizable compound is contained, it is preferable to contain at least a monofunctional acrylamide compound or a monofunctional (meth) acrylate compound. In particular, it is preferable to contain a monofunctional acrylamide compound.
  • polyfunctional radical polymerizable compound examples include a polyfunctional (meth) acrylate compound, a vinyl ether group-containing (meth) acrylate compound, and a polyfunctional (meth) acryloyl group. Examples thereof include isocyanurate-based compounds, polyfunctional (meth) acrylamide-based compounds, polyfunctional urethane (meth) acrylate-based compounds, polyfunctional maleimide-based compounds, polyfunctional vinyl ether-based compounds, and polyfunctional aromatic vinyl-based compounds.
  • polyfunctional (meth) acrylate-based compound examples include ethylene glycol di (meth) acrylate, diethylene glycol di (meth) acrylate, triethylene glycol di (meth) acrylate, tetraethylene glycol di (meth) acrylate, and nonaethylene glycol di.
  • Examples of the vinyl ether group-containing (meth) acrylate compound include 2-vinyloxyethyl (meth) acrylate, 4-vinyloxybutyl (meth) acrylate, 4-vinyloxycyclohexyl (meth) acrylate, and 2- (vinyloxyethoxy) ethyl (meth). ) Acrylate, 2- (vinyloxyethoxyethoxyethoxy) ethyl (meth) acrylate and the like.
  • Examples of the polyfunctional (meth) acryloyl group-containing isocyanurate compound include tri (acryloyloxyethyl) isocyanurate, tri (methacryloyloxyethyl) isocyanurate, and ⁇ -caprolactone-modified tris- (2-acryloyloxyethyl) isocyanurate. And so on.
  • polyfunctional (meth) acrylamide compounds include N, N'-methylenebisacrylamide, N, N'-ethylenebisacrylamide, N, N'-(1,2-dihydroxyethylene) bisacrylamide, N, N'-.
  • polyfunctional (meth) acrylamide compounds include N, N'-methylenebisacrylamide, N, N'-ethylenebisacrylamide, N, N'-(1,2-dihydroxyethylene) bisacrylamide, N, N'-.
  • examples thereof include methylenebismethacrylamide, N, N', N''-triacrylloyldiethylenetriamine and the like.
  • polyfunctional maleimide-based compound examples include 4,4'-diphenylmethane bismaleimide, m-phenylene bismaleimide, bisphenol A diphenyl ether bismaleimide, and 3,3'-dimethyl-5,5'-diethyl-4,4'-.
  • examples thereof include diphenylmethane bismaleimide, 4-methyl-1,3-phenylene bismaleimide, and 1,6-bismaleimide- (2,2,4-trimethyl) hexane.
  • polyfunctional vinyl ether-based compound examples include ethylene glycol divinyl ether, diethylene glycol divinyl ether, polyethylene glycol divinyl ether, propylene glycol divinyl ether, butylene glycol divinyl ether, hexanediol divinyl ether, bisphenol A alkylene oxide divinyl ether, and bisphenol Falkylene oxide.
  • Examples thereof include divinyl ether, trimethylol propane trivinyl ether, ditrimethylol propane tetravinyl ether, glycerin trivinyl ether, pentaerythritol tetravinyl ether, dipentaerythritol pentavinyl ether and dipentaerythritol hexavinyl ether.
  • polyfunctional aromatic vinyl compound examples include divinylbenzene.
  • polyfunctional radically polymerizable compounds may be used alone or in combination of two or more.
  • the radically polymerizable compound (B) contains 2% by mass or more and 70% by mass or less of the radically polymerizable compound (b-1) having a molecular weight of 500 or more.
  • the compound (b-1) is contained in an amount of 5% by mass or more and 65% by mass or less.
  • the ratio of the compound (b-1) is 2% by mass or more, the impact resistance is sufficient.
  • the ratio of the compound (b-1) is 70% by mass or less, the viscosity is sufficiently low and the workability at the time of producing a cured product is excellent.
  • a conventionally known radically polymerizable compound having an ethylenically unsaturated group can be used.
  • the ethylenically unsaturated group include a (meth) acryloyl group, a vinyl group, and a maleimide group.
  • a radically polymerizable compound having a (meth) acryloyl group, particularly a polyfunctional radically polymerizable compound having two or more (meth) acryloyl groups in the molecule can be preferably used.
  • Examples thereof include urethane-based (meth) acrylate oligomers, ether-based (meth) acrylate oligomers, ester-based (meth) acrylate oligomers, and polycarbonate-based (meth) acrylate oligomers.
  • urethane acrylates such as urethane-based (meth) acrylate oligomers are preferable.
  • the compound has one or more of urethane bond, carbonate bond and ester bond.
  • Urethane-based (meth) acrylate oligomers can be obtained by converting the polyols and isocyanate compounds shown below with (meth) acrylate compounds having hydroxyl groups.
  • the ether-based (meth) acrylate oligomer, the ester-based (meth) acrylate oligomer, and the polycarbonate-based (meth) acrylate oligomer are the polyols (polyether polyol, polyester polyol, polycarbonate polyol) and (meth) corresponding to each of the examples below. ) Can be obtained by reaction with acrylic acid.
  • polyether polyol examples include polyethylene glycol, polyoxypropylene glycol, polytetramethylene ether glycol, a copolymer of propylene oxide and ethylene oxide; a copolymer of tetrahydrofuran and ethylene oxide; a copolymer of tetrahydrofuran and propylene oxide; Ethylene oxide adduct of bisphenol A; propylene oxide adduct of bisphenol A and the like can be mentioned.
  • polyester polyol examples include ethylene glycol, propylene glycol, diethylene glycol, dipropylene glycol, 1,5-pentanediol, 3-methyl-1,5-pentanediol, 1,6-hexanediol, and neopentyl glycol.
  • polycarbonate polyol examples include 1,6-hexanediol, 3-methyl-1,5-pentanediol, neopentyl glycol, 1,4-butanediol, 1,5-octanediol, and 1,4-bis- ( Hydroxymethyl) Cyclohexane, 2-methylpropanediol, dipropylene glycol, dibutylene glycol, bisphenol A and other diol compounds, or these diol compounds and ethylene oxide 2 to 6 molar addition reactants, and shorts such as dimethyl carbonate and diethyl carbonate.
  • Examples include polycarbonate polyols composed of reaction products with chain dialkyl carbonates. Commercially available products can be used as the urethane acrylate composed of these. For example, CN9001NS manufactured by Arkema Co., Ltd. can be used.
  • ethylene oxide of these polycarbonate polyols, propylene oxide and polyesterdiol which is an ⁇ -caprolactam or ⁇ -methyl- ⁇ -valerolactone addition reaction product can also be used.
  • isocyanate compounds examples include tolylene diisocyanate, 4,4'-diphenylmethane diisocyanate, hydrogenated 4,4'-diphenylmethane diisocyanate, xylylene diisocyanate, hydrogenated xylylene diisocyanate, hexamethylene diisocyanate, and isophorone diisocyanate.
  • 1,5-naphthalenediocyanate trizine diisocyanate, p-phenylenediisocyanate, transcyclohexane-1,4-diisocyanate, lysine diisocyanate, tetramethylxylene diisocyanate, lysine ester triisocyanate, 1,6,11-undecantriisocyanate, 1,8 -Diisocyanate-4-isocyanate methyl octane, 1,3,6-hexamethylene triisocyanate, bicycloheptane triisocyanate, trimethylhexamethylene diisocyanate and the like are used.
  • Radar polymerization initiator (C) (component (C))
  • a photoradical polymerization initiator or a thermal radical polymerization initiator can be used.
  • Photoradical polymerization initiators are mainly classified into intramolecular cleavage type and hydrogen abstraction type.
  • the bond at a specific site is cleaved by absorbing light of a specific wavelength.
  • a radical is generated at the cleaved site, which serves as a polymerization initiator, and the polymerization of the radical polymerizable compound (B) such as an ethylenically unsaturated compound containing a (meth) acryloyl group starts.
  • the hydrogen abstraction type it absorbs light of a specific wavelength and becomes excited, and the excited species causes a hydrogen abstraction reaction from the surrounding hydrogen donor to generate radicals, which act as a polymerization initiator and radicals. Polymerization of the polymerizable compound (B) begins.
  • an alkylphenone-based photoradical polymerization initiator As the intramolecular cleavage type photoradical polymerization initiator, an alkylphenone-based photoradical polymerization initiator, an acylphosphine oxide-based photoradical polymerization initiator, and an oxime ester-based photoradical polymerization initiator are known. These are of the type in which the bond adjacent to the carbonyl group is alpha-cleaved to produce a radical species.
  • the alkylphenone-based photoradical polymerization initiator include a benzylmethyl ketal-based photoradical polymerization initiator, an ⁇ -hydroxyalkylphenone-based photoradical polymerization initiator, and an aminoalkylphenone-based photoradical polymerization initiator.
  • Specific compounds include, for example, 2,2'-dimethoxy-1,2-diphenylethane-1-one as a benzylmethyl ketal-based photoradical polymerization initiator (Irgacure (registered trademark) 651, manufactured by BASF).
  • Benzylmethyl ketal-based photoradical polymerization initiator Irgacure (registered trademark) 651, manufactured by BASF.
  • ⁇ -hydroxyalkylphenone-based photoradical polymerization initiators 2-hydroxy-2-methyl-1-phenylpropan-1-one (DaroCure 1173, manufactured by BASF), 1-hydroxycyclohexylphenylketone (Irgacure), etc.
  • agent examples include 2-methyl-1- (4-methylthiophenyl) -2-morpholinopropane-1-one (Irgacure 907, manufactured by BASF) or 2-benzylmethyl-2-dimethylamino-1- (4-). Morphorinophenyl) -1-butanone (Irgacure 369, manufactured by BASF) and the like, but are not limited thereto.
  • Acylphosphine oxide-based photoradical polymerization initiators include 2,4,6-trimethylbenzoyldiphenylphosphine oxide (Lucillin TPO, manufactured by BASF), bis (2,4,6-trimethylbenzoyl) -phenylphosphine oxide (Irgacure 819).
  • oxime ester-based photoradical polymerization initiator examples include (2E) -2- (benzoyloxyimino) -1- [4- (phenylthio) phenyl] octane-1-one (Irgacure OXE-01, manufactured by BASF) and the like. However, it is not limited to this.
  • An example of the product name is also shown in parentheses.
  • Examples of the hydrogen abstraction type photoradical polymerization initiator include anthraquinone derivatives such as 2-ethyl-9,10-anthraquinone and 2-t-butyl-9,10-anthraquinone, and thioxanthone derivatives such as isopropylthioxanthone and 2,4-diethylthioxanthone. However, it is not limited to this.
  • photoradical polymerization initiators may be used alone or in combination of two or more. In addition, it may be used in combination with a thermal radical polymerization initiator described later.
  • the amount of the photoradical polymerization initiator added is preferably 0.1 parts by mass or more and 15 parts by mass or less, and more preferably 0.1 parts by mass or more and 10 parts by mass with respect to 100 parts by mass of the radically polymerizable compound (B). It is as follows. When the photoradical polymerization initiator is 0.1 parts by mass or more, the polymerization is sufficient. When the amount of the photoradical polymerization initiator is 15 parts by mass or less, the molecular weight is sufficiently increased, and heat resistance or impact resistance can be sufficiently obtained.
  • the thermal radical polymerization initiator is not particularly limited as long as it generates radicals by heating, and conventionally known compounds can be used.
  • azo compounds, peroxides, persulfates and the like are preferable. It can be exemplified as a thing.
  • examples of azo compounds include 2,2'-azobisisobutyronitrile, 2,2'-azobis (methylisobutyrate), 2,2'-azobis-2,4-dimethylvaleronitrile, and 1,1'-. Azobis (1-acetoxy-1-phenylethane) and the like can be mentioned.
  • peroxide examples include benzoyl peroxide, di-t-butylbenzoyl peroxide, t-butylperoxypivalate and di (4-t-butylcyclohexyl) peroxydicarbonate.
  • persulfate examples include persulfates such as ammonium persulfate, sodium persulfate and potassium persulfate.
  • the amount of the thermal radical polymerization initiator added is preferably 0.1 parts by mass or more and 15 parts by mass or less, and more preferably 0.1 parts by mass or more and 10 parts by mass with respect to 100 parts by mass of the radically polymerizable compound (B). It is as follows. When the amount of the thermal radical polymerization initiator is 0.1 parts by mass or more, the polymerization is sufficient. When the thermal radical polymerization initiator is 15 parts by mass or less, the molecular weight is sufficiently increased, and heat resistance or impact resistance can be sufficiently obtained.
  • the curable resin composition of the present invention may contain various additives as other optional components as long as the object and effect of the present invention are not impaired.
  • the amount of the additive added is preferably 0.05 parts by mass or more and 25 parts by mass or less with respect to 100 parts by mass in total of the components (A), (B) and (C). More preferably, it is 0.1 part by mass or more and 20 parts by mass or less.
  • a resin such as epoxy resin, polyurethane, polychloroprene, polyester, polysiloxane, petroleum resin, xylene resin, ketone resin, cellulose resin, or polycarbonate
  • Engineering plastics such as polytrafluoroethylene, polychlorotrifluoroethylene, polyvinylidene fluoride, fluorine-based oligomers, silicone-based oligomers, polysulfide-based oligomers, soft metals such as gold, silver, and lead, graphite, mo
  • photosensitizers polymerization inhibitors such as phenothiazine and 2,6-di-t-butyl-4-methylphenol, benzoin compounds, acetophenone compounds, anthraquinone compounds, thioxanthone compounds, ketal compounds, benzophenone compounds, and tertiary compounds.
  • An amine compound, a xanthone compound and the like may be added.
  • additives include polymerization initiators, leveling agents, wettability improvers, surfactants, plasticizers, UV absorbers, silane coupling agents, inorganic fillers, pigments, dyes, antioxidants, flame retardants. , Thickener, antifoaming agent and the like.
  • ⁇ Curable resin composition In the composition of the present invention, an appropriate amount of the component (A), the component (B), the component (C), and other optional components, if necessary, is charged in a stirring container, and usually 20 ° C. or higher and 120 ° C. or lower. Preferably, the mixture is stirred at 40 ° C. or higher and 100 ° C. or lower. Then, it can be produced by removing a volatile solvent or the like as needed.
  • the curable resin composition according to the present invention can be suitably used as a modeling material used in the stereolithography method. That is, it is desired by selectively irradiating the curable resin composition of the present invention with active energy rays such as ultraviolet / visible light, electron beam, X-ray, and radiation to supply the energy required for curing. It is possible to manufacture a modeled object having the shape of.
  • a cured product can be produced by curing the curable resin composition of the present invention using a known method such as activation energy ray irradiation or heat irradiation.
  • the active energy ray include ultraviolet / visible light, electron beam, X-ray, and radiation.
  • ultraviolet / visible light having a wavelength of 300 nm or more and 450 nm or less can be preferably used in terms of easy availability and compatibility with a photoradical polymerization initiator.
  • an ultraviolet / visible light laser for example, Ar laser, He-Cd laser, etc.
  • a mercury lamp for example, a mercury lamp, a xenon lamp, a halogen lamp, a fluorescent lamp, or the like
  • the laser light source is preferably adopted because it can raise the energy level, shorten the molding time, and can obtain high molding accuracy due to excellent light collecting property.
  • the curing method can be appropriately selected according to the type of radical polymerization initiator contained in the curable resin composition. Further, the curing method may be used alone or in combination of two or more.
  • the curable resin composition of the present invention can be suitably used as a modeling material for a stereolithography method.
  • the three-dimensional model obtained by curing the curable resin composition of the present invention can be produced by using a known stereolithography method and apparatus.
  • Typical examples of a preferable stereolithography method include (i) a step of arranging a photocurable resin composition with a predetermined thickness, and (ii) slice data generated from three-dimensional shape data of a three-dimensional model (modeling model). Based on this, it is a method including a step of irradiating a photocurable resin composition with light energy to cure it a plurality of times, and is roughly divided into two types, a free liquid level method and a regulated liquid level method.
  • FIG. 1 shows a configuration example of the stereolithography apparatus 100 using the free liquid level method.
  • the stereolithography apparatus 100 has a tank 11 filled with a liquid photocurable resin composition 10. Inside the tank 11, a modeling stage 12 is provided so as to be driveable in the vertical direction by a drive shaft 13.
  • the irradiation position of the active energy ray 15 for curing the photocurable resin composition 10 emitted from the light source 14 is changed by the galvanometer mirror 16 controlled by the control unit 18 according to the slice data, and the surface of the tank 11 is changed. It is scanned. In FIG. 1, the scanning range is indicated by a thick broken line.
  • the thickness d of the photocurable resin composition 10 cured by the active energy rays 15 is a value determined based on the setting at the time of generating slice data, and the accuracy of the obtained modeled object 17 (three-dimensional shape of the article to be modeled). Affects data reproducibility).
  • the thickness d is achieved by the control unit 18 controlling the drive amount of the drive shaft 13.
  • the control unit 18 controls the drive shaft 13 based on the setting, and the photocurable resin composition having a thickness d is supplied onto the stage 12.
  • the liquid curable resin composition on the stage 12 is selectively irradiated with active energy rays based on slice data so that a cured layer having a desired pattern can be obtained, and a cured layer is formed.
  • the uncured curable resin composition having a thickness d is supplied to the surface of the cured layer.
  • the active energy rays 15 are irradiated based on the slice data, and a cured product integrated with the previously formed cured layer is formed. By repeating this step of curing in layers, the desired three-dimensional model 17 can be obtained.
  • Examples of the active energy beam used for manufacturing include ultraviolet rays, electron beams, X-rays, and radiation. Among them, ultraviolet rays having a wavelength of 300 nm or more and 450 nm or less are preferably used from an economical point of view.
  • an ultraviolet laser for example, Ar laser, He-Cd laser, etc.
  • a mercury lamp for example, a mercury lamp, a xenon lamp, a halogen lamp, a fluorescent lamp, or the like can be used.
  • the laser light source is preferable in that the energy level can be increased, the modeling time can be shortened, the light collecting property is excellent, and high modeling accuracy can be obtained.
  • the active energy is focused in dots or linearly like laser light.
  • the line may be irradiated by a pointillism method or a line drawing method. Further, a method of irradiating the uncured layer with active energy rays in a planar manner may be adopted through a planar drawing mask formed by arranging a plurality of micro light shutters such as a liquid crystal shutter or a digital micromirror shutter.
  • the stage 12 of the stereolithography device 100 of FIG. 1 is provided so as to pull up the modeled object above the liquid level, and the light irradiation means is provided below the tank 11. It becomes a composition.
  • Typical modeling examples of the regulated liquid level method are as follows. First, the support surface of the support stage provided so as to be able to move up and down and the bottom surface of the tank containing the curable resin composition are installed so as to be at a predetermined distance between the support surface of the support stage and the bottom surface of the tank. A curable resin composition is supplied.
  • the curable resin composition between the stage support surface and the bottom surface of the tank is selectively illuminated by a laser light source or a projector according to the slice data. Is irradiated. By irradiation with light, the curable resin composition between the stage support surface and the bottom surface of the tank is cured, and a solid cured resin layer is formed. After that, the support stage is raised and the cured resin layer is peeled off from the bottom surface of the tank.
  • the molded product thus obtained is taken out of the container and washed if necessary to remove the unreacted curable resin composition remaining on the surface thereof.
  • the cleaning agent include alcohol-based organic solvents typified by alcohols such as isopropyl alcohol and ethyl alcohol; ketone-based organic solvents typified by acetone, ethyl acetate, methyl ethyl ketone and the like; aliphatic organic solvents typified by terpenes. Can be used. After removing the unreacted curable resin composition, post-cure by active energy rays or heat (heat treatment) may be performed, if necessary.
  • the surface of the modeled object and the unreacted curable resin composition remaining inside can be cured, the stickiness of the surface of the modeled object can be suppressed, and the initial strength of the modeled object can be suppressed. Can be improved.
  • B-1-1 Bifunctional urethane acrylate; "CN9001NS” (manufactured by Arkema Co., Ltd., weight average molecular weight (measured value): 5.4 x 10 3 )
  • B-1-2 Bifunctional urethane acrylate; "KAYARAD UX-4101” (manufactured by Nippon Kayaku Co., Ltd., weight average molecular weight (measured value): 6.5 x 10 3 )
  • B-1-3 Bifunctional urethane acrylate; "UA-122P” (manufactured by Shin Nakamura Chemical Industry Co., Ltd., weight average molecular weight (measured value): 2.2 ⁇ 10 3 )
  • B-1-4 Bifunctional Polycarbonate Diol Diacrylate; "UM-90 (1/3) DA” (manufactured by Ube Industries, Ltd., weight average molecular weight (measured value): 2.7 ⁇ 10 3 )
  • C-1 Photoradical generator; "Irgacure819” (manufactured by BASF)
  • the molecular weight distribution is divided by the holding time corresponding to the molecular weight of 500 derived from the standard polystyrene-equivalent calibration curve, and the ratio of the region area (Y) having a molecular weight of 500 or more to the total region area (X) (Y / X ⁇ 100 [%). ]), A compound ratio having a molecular weight of 500 or more was obtained.
  • Viscosity of curable resin composition Viscosity was measured by rotary rheometer method. Specifically, it was measured as follows using a viscoelasticity measuring device (Physica MCR302, manufactured by Anton Pearl Co., Ltd.).
  • a measuring device equipped with a cone plate type measuring jig (CP25-2, manufactured by Anton Pearl Co., Ltd .; 25 mm diameter, 2 °) is filled with about 0.5 mL of a sample and adjusted to 25 ° C. Under the constant shear rate condition of 50s-1, the data was measured at a data interval of 0.1 seconds, and the value at 0.1 seconds was taken as the viscosity.
  • the curable resin composition used for three-dimensional modeling is preferably 2,500 mPa ⁇ s or less.
  • the radically polymerizable compound forming the shell layer (17.5 parts by mass of methyl methacrylate (MMA), 17.5 parts by mass of acryloylmorpholine (ACMO)), and 0.1 parts by mass of cumenehydroperoxide.
  • the radical-polymerizable compound was graft-polymerized on the surface of the polybutadiene rubber particles by continuously adding the mixture over 2 hours. After completion of the addition, the reaction was terminated with further stirring for 2 hours to obtain an aqueous dispersion of core-shell type rubber particles having a polybutadiene rubber as a core layer and a copolymerized polymer having a heterocyclic group as a side chain as a shell layer.
  • the aqueous dispersion of the core-shell type rubber particles obtained as described above was put into 450 parts by mass of acetone and mixed uniformly. After centrifuging at a rotation speed of 12000 rpm and a temperature of 10 ° C. for 30 minutes using a centrifuge, the supernatant was removed. Acetone was added to the precipitated core-shell rubber particles and redispersed, and the mixture was centrifuged and the supernatant was removed twice under the same conditions as described above to obtain an acetone dispersion of the core-shell rubber particles A-1.
  • the average particle size of the core-shell type rubber particles A-1 was 0.30 ⁇ m.
  • Example 1 An acetone dispersion of core-shell type rubber particles A-1 (solid content 18 parts by mass) and B-1-1 (30 parts by mass), B-2-2 (40 parts by mass), B-2 as radically polymerizable compounds. -3 (30 parts by mass) and C-1 (2 parts by mass) as a radical polymerization initiator were blended and mixed uniformly. A curable resin composition was obtained by removing acetone, which is a volatile component, using a rotary evaporator.
  • a cured product was prepared from the prepared curable resin composition by the following method. First, a mold having a length of 80 mm, a width of 10 mm, and a thickness of 4 mm was sandwiched between two pieces of quartz glass, and a curable resin composition was poured into the mold. The poured curable resin composition is irradiated with ultraviolet rays of 5 mW / cm2 alternately from both sides of the mold four times for 120 seconds with an ultraviolet irradiator (manufactured by HOYA CANDEO OPTRONICS Co., Ltd., trade name "LIGHT SOURCE EXITURE 3000"). bottom. The obtained cured product was placed in a heating oven at 50 ° C. for 1 hour and heat-treated in a heating oven at 100 ° C. for 2 hours to obtain a test piece having a length of 80 mm, a width of 10 mm and a thickness of 4 mm. rice field.
  • Table 2 shows the viscosity of the curable resin composition and the Charpy impact strength of the cured product.
  • Examples 2 to 14 Comparative Examples 1 to 5> A curable resin composition and a cured product were obtained in the same manner as in Example 1 except that the components shown in Table 2 were used. Table 2 shows the viscosity of the curable resin composition and the Charpy impact strength of the cured product.

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  • Chemical & Material Sciences (AREA)
  • Health & Medical Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Organic Chemistry (AREA)
  • Graft Or Block Polymers (AREA)
  • Macromonomer-Based Addition Polymer (AREA)

Abstract

La présente invention concerne une composition de résine durcissable ayant une faible viscosité, ce qui permet d'obtenir un produit durci ayant une excellente résistance aux chocs. Cette composition de résine durcissable contient : des particules de caoutchouc de type cœur-écorce (A) ; un composé polymérisable par voie radicalaire (B) ayant un ou plusieurs groupes fonctionnels polymérisables par voie radicalaire dans une molécule ; et un initiateur de polymérisation radicalaire (C). Les particules de caoutchouc de type cœur-écorce (A) ont chacune une couche de cœur et une couche d'écorce qui contient un polymère ayant une structure hétérocyclique. Si la quantité totale de tous les composants de la composition de résine durcissable est de 100 % en masse, la teneur en composé polymérisable par voie radicalaire (B) est de 50 à 99 % en masse, dont 2 à 70 % en masse d'un composé polymérisable par voie radicalaire (b-1) ayant un poids moléculaire de 500 ou plus.
PCT/JP2021/015915 2020-04-21 2021-04-19 Composition de résine durcissable et procédé de fabrication d'un objet tridimensionnel au moyen de cette composition WO2021215407A1 (fr)

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Citations (8)

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Publication number Priority date Publication date Assignee Title
JP2004051665A (ja) * 2002-07-16 2004-02-19 Mitsubishi Rayon Co Ltd 光学的立体造形用樹脂組成物、及び立体造形物
JP2006002110A (ja) * 2004-06-21 2006-01-05 Mitsubishi Rayon Co Ltd 光学的立体造形用樹脂組成物、及び立体造形物
JP2019183028A (ja) * 2018-04-12 2019-10-24 三菱ケミカル株式会社 光造形用樹脂組成物
JP2019183133A (ja) * 2018-04-16 2019-10-24 キヤノン株式会社 硬化性樹脂組成物およびそれを用いた立体物の製造方法
WO2020085166A1 (fr) * 2018-10-22 2020-04-30 キヤノン株式会社 Composition de résine durcissable et objet durci obtenu à partir de celle-ci
WO2020246489A1 (fr) * 2019-06-07 2020-12-10 キヤノン株式会社 Composition de résine durcissable, produit durci associé et procédé de fabrication d'article tridimensionnel
JP2020200437A (ja) * 2018-10-22 2020-12-17 キヤノン株式会社 硬化性樹脂組成物、およびその硬化物
JP2020200450A (ja) * 2019-06-07 2020-12-17 キヤノン株式会社 硬化性樹脂組成物とその硬化物、及び立体物の製造方法

Patent Citations (8)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2004051665A (ja) * 2002-07-16 2004-02-19 Mitsubishi Rayon Co Ltd 光学的立体造形用樹脂組成物、及び立体造形物
JP2006002110A (ja) * 2004-06-21 2006-01-05 Mitsubishi Rayon Co Ltd 光学的立体造形用樹脂組成物、及び立体造形物
JP2019183028A (ja) * 2018-04-12 2019-10-24 三菱ケミカル株式会社 光造形用樹脂組成物
JP2019183133A (ja) * 2018-04-16 2019-10-24 キヤノン株式会社 硬化性樹脂組成物およびそれを用いた立体物の製造方法
WO2020085166A1 (fr) * 2018-10-22 2020-04-30 キヤノン株式会社 Composition de résine durcissable et objet durci obtenu à partir de celle-ci
JP2020200437A (ja) * 2018-10-22 2020-12-17 キヤノン株式会社 硬化性樹脂組成物、およびその硬化物
WO2020246489A1 (fr) * 2019-06-07 2020-12-10 キヤノン株式会社 Composition de résine durcissable, produit durci associé et procédé de fabrication d'article tridimensionnel
JP2020200450A (ja) * 2019-06-07 2020-12-17 キヤノン株式会社 硬化性樹脂組成物とその硬化物、及び立体物の製造方法

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